Linoleum composition



Patented New. E3, 3945 Paul 0. Powers, Manheim Township, Lancaster Gountaga, assignor to Armstrong Cork cm om. Vania caster, Pa, a corporation of Pennsyl- V o No Drawing. Application August 20,1942,

' SerialNo. 455,437

12 Claims. (Cl. 260-49) ula.

R\ /R1 @"Q HO OH in which R and R may be the same or diflerent substituents selected from the group consisting of hydrogen, halogen, alkyl,- or together they may represent a cyclic aliphatic hydrocarbon and as claimed.

The cements used in making linoleum usually contain as a characteristic ingredient a substance m as linoxyn; a product of the oxidation of drying oils. In linoleum manufacture, lino is generally made by oxidizing linseed oil, by exposure to the air. In oxidizing linseed oil by air blowing, the ofl is thickened or bodied.

There are various well-known ways of making linoleum cement. In the so-called scrim or shed oil process the requisite oxidation and thickening of the oil is brought about by allowing the oil to slowly drip over muslin sheets hung in festoons in sheds for bringing it into contact with atmospheric oiwgen. In the so-called Walton process the oil is heated with driers, and air is blown through. In both processes, a semi-solid, plastic mass results which includes substantial portions of oxidized, but uncoagulated, oil and linoxyn. Linoleum cements usually comprise this partially processed drying oil and a resin such as rosin, ester gum, kauri gum, and the Ordinarily linoleum cements comprise 05% to 85% partially processed drying oil and 15% to 35% resin. The drying oil generally employed is linseed oil but other oils such as soya oil and the like may be used. The product mown to the art as linoleum is prepared by adthese linoleum cements, comprising procoil and resin, with a suitable filler such as cork, wood flour and the like and applying the e to a nin lap foundation. A similar product, mown as Linoflorl' is made by applying such composition to a saturated felt foundation. It is essential, that the final products contain-a completely oxidized or coagulated oil or linoleum cement. I It is,.thereiore. necessary that the product undergo a further process of polymeriaation and possibly some oxidation, depending T211 cal; all as more fully hereinafter set forth upon the type of cement used, to render it suiilciently hard to be commercially serviceable. This further process is necessarily carried out after the product of the mixing operation has been consolidated. This process is usually referred to as seasoning, storing, curing or maturing, and is a hereinafter referred to as maturing. The maturing stage is usually'carried out in a warm stove and is expensive, as it takes a considerable time, several weeks or so, to mature the linoleum sufiiciently for commercial usage.

Various ingredients have been added to linoleum compositions for the purpose of shortening the time required for maturing the linoleum mix. Among the materials which have been tried have been certain condensation products of formaldehyde with certain phenols and cresols. However. these products heretofore used as hardenin diluents in linoleum compositions possess one or more of the decided disadvantages of being highly volatile and, therefore, their presence in the stoves and in the mix is a definite health hazard;-' of being substantially nonreactive and having no appreciable effect on the maturing time when used in relatively small quantities and having only a slight eilect when used in relatively large proportions such as 20% or more of the cement; and, of showing no appreciable effect upon the maturing oi the mix at the temperatures at which linoleum is matured, that is, temperatures of about 160 F. to about 200 F.

I have found that dihydroxy benzophenone and certain other phenols which may be generically termed di (hydroxaryl) methanes may be condensed with various aldehydes or aldehyde yielding compounds, and the reactive condensation products formed are insoluble in rawdrying oil but are-soluble in oxidized drying oil and may be successfully incorporated into a linoleum cement to greatly accelerate the maturing of the linoleum mix. These phenolic resins are not volatile at the temperatures employed in maturing the mix and, therefore, there is no possibility of dangerous fumes and gases emitting from the stoves. Further, these accelerators, even when used in relatively small amounts, greatly accelerate the maturing of the linoleum mix at the temperatures commonly used in the storing operation, that is, they reduce the maturing time required to obtain the necessary hardness.

The'phenols, other than benzophenone, suitable for the preparation of these resinous accelerators for me in linoleum compositions are herein designated by the generic expression di (hydroxyaryl) methanes and may be generically represented b the following structural formula:

in which R and R may be the same or different linoleum cement at the low maturing temperasubstituents selected from the group consisting of tures to greatly shorten the maturing time. hydrogen, halogen, alkyl, or together they may In practicing my invention, a small amount of represent a cyclic aliphatic hydrocarbon radical these phenolic condensation products may be hereinafter designated as an alicyclyl radical. 5 added to the linoleum compositions known in the The hydrogen atoms in the nuclei may be substiart. The compositions thus prepared may then tuted by halogen, alkyl, aryl, aralkyl, or hydroxyl be applied to any suitable backing material and groups. .The nuclei should be so substituted, processed and matured in any manner now comhowever, that at least two reactive positions remonly used or known to the art. Linoleum mixes main open in each nucleus. Such reactive posicontaining the accelerators of my invention are tions are generally ortho or para with respect to matured at a greater saving of time than are the the hydroxyl groups in the nuclei. These benzocompositions heretofore known.

phenones and di (hydroxyaryl) methanes having Although the compositions of my invention are at least two reactive positions available in the by no means limited to the proportion of accelernuclei which nuclei are linked through an ullator added, it is advantageous that the accelerphatic or substituted aliphatic radical exhibit the ator be present in relatively small amounts. 1' unique properties which render them suitable for have found it particularly advantageous to cmhe P p r ion of the resinous accelerators of ploy the reactive phenol-aldehyde condensation this invention. These-d1 (hydroxyaryl) methanes products in amounts equal to about 1% to about are also known as "bis-arylol methanes." These 10% of the weight of the linoleum cement. Should benzophenones and di (hydroxyaryl) methanes. less than 1% of the accelerator be employed in are known as bis-phenols." These compounds the cement, no substantial acceleration of maturmay be further defined as the reaction product ing is obtained. The use of more than 10% of of a carbonyl compound, which may be reprecondensation product is somewhat disadvantasented by the following generic formula: geous in that, with more than 10% of the con- R densation product present, there is a tendency for the cement to harden too rapidly resulting in a final product which may be too hard and R brittle to be satisfactorily used as a floor cover- I :0 ing. For instance. upon the addition of 5% of in whlchRmaybeasubstituent selected from the my accelerator to a linoleum commiuon group consisting or hyd and alkyl and uirin from 21 to 24 da s for maturing the substituent selected from the group iaturi ng time was reduced to about 11 /2 days. slstmg or alkyl and amlkyl' with phenol the efl'ect of the accelerator is partially dependhavmg at least three reactive positions available out on the percentage of accelerator used and the in each nucleus. Example of such bis-phenols constituents of the mix.

are following: The addition of accelerator to the linoleum Beta,beta-bis(4-hydroxy-phenyl)-propane take Place at my time during B1s (4 hyd1-oxy pheny1) .methane the consolidation of the linoleum mix, provided, 4,4' d1hydmxy benzphenne 40 of course, that said addition is made prior to B t b t ,(2 4'-d1 1 h 1 the maturing step. Particularly advantageous Beta'beta b1s(2 hydroxy pheny1)-promne results are obtained, however, when the acceler- Bis (2 hydmxy pheny1) methane ator is added to the linoleum cement prior to B1s (4 hydmxy 2 methy1 pheny1) methane the consolidation of the cement and fillers. When netmbetvbisgumydmxpz methy1 pheny1) bu such procedure is followed, the accelerator is more readily dispersed throughout the linoleum cet t -b ,4' djhydrox m 1) m ment and therefore is more effective in reducing y p y pen the maturing time of the linoleum mix.

To produce the phenolic resins which are added The following examples, in which all proporto linoleum compositions within the scope of my tions given are by weight, illustrate various speinvention, any of the di (hydroxy ryl) methane ciflc embodiments of my invention. These exor any mixture of them may be reacted with an amples are given merely by way of illustration aldehyde, such as formaldehyde, paraformalde-' and not by limitation.

hyde, acetaldehyde, benzaldehyde, furfural, or al- Example 1 dehyde yielding compositions such as hexamethylenetetramine, aldehyde ammonia, and the like, or A mixt r of 300 Parts of formalin (40% y mixtures of these compositions. The terms "alweight formaldehyde). 230 parts of beta. ta-bis dehyde" and formaldehyde as used in this speco y-p eny1) -propane and pa ts of ification and the appended claims are meant to ium hydroxide was heated for three hours at include both the aldehyde-and any compositions 00 8 p t r of 75 C. The condensed resin which yield the aldehyde at the reaction condi- W 8 separated from the water after acidlfyi lat tions employed during the condensation. r00111 temperature The pr ct thus formed As the benzophenones and di (hydroxyaryl) was added to about 1.500 parts of linoleum cement methanes used to produce my phenolic resins mlde y m nin 75% partially processed linhave at least two reactive positions available in seed oil and 25% rosin in an internal mixer and each of the linked nuclei, or a total of four reita d until mo eneous.

active positions in each molecule, relatively large Example 2 amounts of aldehyde may be used. At least three v and preferably about 4 mols of aldehyde are re- A mixture of 244 parts of 4,4'-dihydroxyacted with one mol of phenol at a temperature 7 0 behzophenone md'300 P rts of formalin (40% by not over 100 C. to produce a soft, reactive resin. weight formaldehyde) and 10 par of sodium When such a reactive resin is added to the cehydroxide were heated for live hours at a temmentinthe linoleum composition andthe 'compnperature of about 90 C. The batch was then sition is then matured, the reactive resin concooled to room temperature, acidified and the denses with itself and possibly reacts with the water was removed. The condensation product was added to about 2,000 parts or linoleum Example 3 A mixture of 202 parts of bis-(4-hydroxyphenyl) -methane and 270 parts of formalin (40% by weight formaldehyde) and 7 parts of sodium hydroxide was heated for three hours at a temperature of 75 C. The mixture was then cooled and acidified at room temperature. Th water present in the batch was then removed. The reaction product thus formed was added to about 1,800 parts of linoleum cement made by combining 85% partially processed linseed oil and rosin, and the resulting mixture was milled on difi'erential rolls until homogeneous.

In all of the foregoing examples, a relatively large amount of aldehyde is used and reacts with the benzophenones or di (hydroxyaryl) methane at 'the usual maturing temperatures. During the maturing of the linoleum composition, there is apparently considerable condensation of the resin with itself and possibly a reaction of the resin with the linoleum cement. All of these resins are further characterized by being soluble in oxidized drying oil but insoluble in raw drying oil.

It should be understood that any aldehyde or aldehyde yielding material which is capable of reacting with the substituted phenols disclosed may be employed in the preparation of the phenol aldehyde condensation products. Likewise, other substituted phenols falling within the generic classification set out earlier in the specification may be substituted for theparticular phenols specifically disclosed in the examples without departing from the scope of the invention. Also, the reactive condensation products ma be added to advantage to any linoleum composition known to the art.

maturing accelerator for said cement, said accelerator comprising a reactive condensation product of about 3 to about 4 mols of an aldehyde and about 1 mol oi-a di (hydrnxyaryl) methane. 3. A linoleum composition in accordance with claim 2 in which the aldehyde is formaldehyde.

4. A linoleum composition which includes a linoleum cement containing an oxidized siccative oil and resin and about 1% to about 10% of a maturing accelerator for said cement, said accelerator comprising a reactive condensation product of about 4 mols of formaldehyde and 1 moi of a di (hydroxyaryl) methane.

5. A linoleum composition which" includes a linoleum cement containing an oxidized siccative oil and resin and about 1% to about 10% o1 a maturing accelerator for said cement, said accelerator comprising a reactive condensation product of about 3 to about 4 mols of an aldehyde and 1 moi of 4,4'-dihydroxy-benzophenone.

6. A linoleum composition which includes a linoleum cement containing an oxidized siccative oil and resin and about 1% to about 10% 01. a

' maturing accelerator for said cement,-sa.id accelerator comprising a reactive condensation product of about 3 to about 4 mols of an aldehyde and 1 mol of beta, beta-bis (4-hydroxy-phenyD-prop p 7. A linoleum, composition which includes a linoleum cement containing an oxidized siccative oil and resin and about 1% to about 10% of a maturing accelerator for said cement,.said accelerator comprising a reactive condensation product of about 3 to about 4 mols of an aldehyde and 1 mol of his (4-hydroxy-phenyD-methane.

8. A linoleum composition which includes a linoleum cement containing an oxidized siccative .oil and resin and about 1% to about 10% of a maturing accelerator for said cement, said accel-- erator comprising a reactive condensation product of about 3 to about 4 mols of formaldehyde and 1 mol of his (4-hydroxy-phenyl) -methane.

The use of the compositions of the invention greatly reduces the time necessary to completely mature the linoleum mix and thereby results in valuable saving in time and materials in the linoleum making process.

These linoleum compositions yield final products which are characterized by excellent wear resistance, flexibility, and resiliency. They may 0 made without departing lrom the spirit or the invention and it is to be understood that the invention is limited only by the appended claims.

I claim: p

1. A linoleum composition which includes a linoleum cement containing an oxidized siccative oil' and resin and about 1% to about 10%01 a maturing accelerator for said cement, said accelerator comprising a reactive condensation product of an aldehyde and a compound selected from. the group consisting of dihydroxy benzophenone and d1 (hydroxyaryl) methane, said condensation product being characterized by insolubility in raw drying oiland solubility in oxidized drying oil.

2. A linoleum composition which includes a linoleum cement containing an oxidized siccative oil and-resin and about 1% to about 10%.0'1 a 9. A linoleum composition which includes a linoleum cement containing an oxidized siccative oil and a resin and about 1% to about 10% of a maturing accelerator for said cement, said accelerator comprising a reactive condensation product of about 3 to about 4 mols of formaldehyde and 1 mol of 4,4'-dihydroxy-benzophenone.

10. A linoleum composition which includes a linoleum cement containing an oxidized siccative oil and resin and about 1% to about 10% of a -maturing accelerator for said cement, said accelerator comprising a reactive condensation prodto about 4 mols oi formaldehyde not of about 3 -hy r y-phenyl) and l molof beta, beta-bis propane.

11. A linoleum composition which includes a linoleum cement containing an oxidized siccative oil and resin and about 1% to about 10% o! a maturing accelerator for said cement. said accelerator comprising a reactive condensation prod- 1 not of about 3 to about 4 mols of an aldehyde and 1 mol of a compound selected from the group consisting of dihydroxy benzophenone and e di (hydroxyaryi) methane.

12. A linoleum composition in accordance with claim 1 in which the oxidized siccative oil is oxidized linseed oil, in which the resin is rosin, and in which the reactive condensation product is formed by reaction or about 4 mols ot formaldehyde with 1 moi of his (4-hydroxy-phenylimethane.

PAUL O. POWERS. 

